Unsaturated esters of halo-aryloxy alcohols



Patented Feb. 5, 1946 ESTERS F HALO-ARYLOXY ALCOHOLS Gerald H.Coleman'and Bartholdt C. Hadler, Midland, Mich., assignors to The DowChemical Company, Midland, Mlch., a corporation of Michigan l IUNSATURATED No Drawing. Application February 17, 1942,

Serial No. 431,292

6 Claims.

This invention concerns esters of halo-aryloxysubstituted alcohols withcertain unsaturated aliphatic dicarboxylic acids, said esters having thegeneral formula:

x, r v I o wherein X represents a halogen substituent selected from thegroup consisting of chlorine and bromine; R1 represents a lower alkyleneradical containing at least two-carbon atoms, the free valences of saidradical being borne by difierent carbon atoms; R represents an aliphatic.hydrocarbon radical containing not more than ten carbon atoms and atleast one ethylenic linkage; and n represents the number ofsubstituentson the aryl nucleus and is not greater than 4. 'Ihe phenylradical may contain, in addition to-the halogen substituents, otherneutral substituents such as an alkyl radical. All such esters arehigh-boiling liquids or crystalline solids which are substantiallyinsoluble in water but are readily soluble in many organic solvents.They are useful as plasticizing and modifying agents for vinyl resins,e. g. polystyrene, and cellulose derivative (e. g. ethyl cellulose,cellulose acetate, etc.) compositions.

The unsaturated esters of the present class are conveniently prepared byesterifying a haloaryloxy-substituted alcohol, e. g. beta-(2-chlorophenoxy) ethanol, beta (2.4 dibromophenoxy) propanol, etc.,with an aliphatic dicarboxylic acid which contains not more than tencarbon atoms and at least one ethylenic linkage in the aliphaticresidue, e. g. maleic acid, glutaconic acid, etc. The reaction may becarried out by heating at a suitable temperature, e. g. about 60-150 0.,a mixture of the alcohol with approximately one chemical equivalent ofthe unsaturated carboxylic acid and a small proportion of anesterification catalyst, e. g. approximately 0.01-0.04 molecularequivalent of a strong acid, such as sulfuric or benzene sulfonic acid.Water is formed in the reaction and, if desired, a waterimmiscibleorganic solvent, such as benzene or toluene, may be added to thereaction mixture for the purpose of promoting distillation and removalof the water during the esterification. Upon completion of the reaction,the mixture is treated with sumcient alkali to neutralize any free acid,washed with water, and the ester product is separated and purified byfractional distillation or crystallization.

'6 The following examples are illustrative of the preparation of severalof the esters of the present class, but are not tobe construed aslimiting the invention:

Example 1' A mixture of 1&5 grams (0.6 mol) of beta-(2.4.6-trichlorophenoxy) ethanol, 40 grams (0.25 mol) of maleic acid, 5grams of benzene sulfonic acid, and 250 cc. of benzene was heated to atemperature of about 82 C. for about 2 hours, water being distilled fromthe mixture as formed. The reaction mixture was cooled and treated witha saturated solution of sodium. bicarbonate. An emulsion which formedduring the latter treatmentwas broken by the addition of 250 cc. ofbenzene. The benzene solution was then treated with two 250 cc. portionsof distilled water. .The benzene was removed by distillation and .thecrude ester was crystallized from a petroleum fraction of boilingrange'60-l00 C. The purified ester, di-(2.4.6-trichlorophenoxyethyDmaleate, had a melting point of 76.5-78 C. and has the formula:

filed December l, 193% 'moved under vacuum and the residual benzene wasremoved by passing a stream of air through the warm material. The esterproduct, di-(beta- (2-bromo-4-ethyl-phenoxy)ethyDmaleate, is a viscousliquid and has a specific gravity at ive index at of 1.562() and has theformula:

of 1.4180- and a retract Br l y n-i-o-n CHr-CH QOQQBB V Otherunsaturated halo-aryloxy alkyl esters of the present class may bepreparedby thegen eral method illustrated by the foregoing'g amples; forexample, 4'-chlorophenoxy propanol may be reacted with glutaconic acidto produce di- (4-.-chlorophenoxy 1 propyliglutac nate, 2-bromophenoxyethanol withoitraconie acid to pro' duce ieQ- IOm DhEIlQXY ethyl)eitraeonate; 24-: diehlorophenoxy 'p p ol with itaeenie aeid to produ edi( di h1erophenexy propsfliitw senate, :2.; :-6tri bremoehenoxy ethanolwith inesaeeniei'aeid to premiere di tz-ifi-tribreme phenoxyethyDmesaconate, 2-chloro-avtertiary butyl phenoxy ethano1- .with maleicacid to produce d -eh1oro 4 tertiary 'b tyi rpheno y ethyl) maleate, 2.4-.die1iiore-6 see! hutyi phenexy ethanol with iumarie acid to producedi-lli-dialcohol radical contains at least two andless than four carbonatoms none of which carbon atoms has more than a single oxygen atom atvwherein X represents a halogen substituent se-- lected from the groupconsisting of chlorine and Irr-omine; 1% represents an aliphatichydrocarBon' chiom-fi-sea butyl phenoxy ethylii uinarat ete- 7 lineapplication is a'eontinuation inepartfei our copendin application se ialNo, 321.31% filed 40 February 28 719i!) which, in turn, is acontinuation-impart. of applicati n Serial No. 137.655,

We claim: A v d l, A neutral esterof a stituted lower alcoho where n thearomatic radical is amone cyelic radical ofthe benzene series, thehalogen is selected f om the cla s eonhlorine andrhremine. and saidlower haio-aryloxy-sub tached thereto, and an aliphatic dicarboxylicacid containing not more than 10 carbon atoms and a single ethyleniclinkage in the aliphatic radical. s

2. A neutral ester of a haloaryloxy substituted alcohol and anunsaturated aliphatic dicarboxylic acid, said ester having thegeneralformula M awit radical containing not more than 10 carbon atoms and asingle ethylenic linkage, and n represents integer not greater than 4.

."fi A neutral ester of a chloroaryloxy-substituted alcohol and anunsaturated aliphatic di- 7 ,earhoxylic acid, said ester havin mi g thegeneral wherein it represents an aliphatic hydrocarbon radical.containing not more than 10 carbon atoms and a single ethylenic linkage,and n represents an integer not greater than 4.

4. A neutral ester of a broinoaryloXy-sub stituted alcohol and anunsaturated aliphatic dicarboxylic acid, said ester having the generalfor- (2 -bremo-4'-ethyl rieaoxyiethyn F GERALD neetmen:

BARTHQLDT e. HADLERJ 7 h eph n xw e hyl)

